Novel large ring compounds

ABSTRACT

A series of mono, bi and tricarbocyclic compounds, most of which have olefinic unsaturation in the ring, which may or may not have substituents thereon. While the bi and tricyclic rings may be unsubstituted, these compounds which have olefinic unsaturation, particularly multiple olefinic unsaturation, are polymerizable and copolymerizable in known polymerization systems. They are particularly good crosslinking agents. These compounds are further useful in the sense that they can be cleaved oxidatively, to corresponding carboxylic acids, aldehydes and/or alcohols which have known utility in the plasticizer and detergent arts. The compounds which do not have olefinic unsaturation can also be oxidatively cleaved to produce oxygenated, e.g., acid, alcohol or aldehyde, compounds having known utility.

United States Paten Wilke et a1.

NOVEL LARGE RING COMPOUNDS Inventors: Giinther Wilke; Paul Heimbach,

both of Mulheim (Ruhr), Germany Studiengesellschaft Kohle m.b.H.,Mulheim (Ruhr), Germany Filed: Apr. 22, 1974 Appl. No.: 463,088

Related US. Application Data Division of Ser. No. 109,949, Jan. 26,1971, Pat. No. 3,849,506, which is a continuation of Ser. No. 843,220,July 18, 1969, Pat. No. 3,586,727, and a continuation-in-part of Ser.Nos. 845,901, July 29, 1969, Pat. No. 3,629,347, and Ser. No. 845,904,July 29, 1969, abandoned, said Ser. No. 845,901, and Ser. No. 845,904,each is a continuation-in-part of Ser. No. 582,775, Sept. 27,1966,abandoned.

Assignee:

Foreign Application Priority Data Sept. 29, 1965 Germany 2443912 US. Cl.260/666 PY; 260/666 B Int. Cl. C07C 13/00 Field of Search 260/666 B, 666PY References Cited UNITED STATES PATENTS 12/1960 Wilke 260/666 B 4/1961Wilke et al 260/666 B 9/1962 Wilke 260/666 B OTHER PUBLICATIONS Wilke,Angew. Chem. 75, pp. 10-20, 1963.

Primary Examiner-Veronica OKeefe Attorney, Agent, or Firm-Burgess,Dinklage & Sprung [57] ABSTRACT A series of mono, bi and tricarbocycliccompounds, most of which have olefinic unsaturation in the ring, whichmay or may not have substituents thereon. While the bi and tricyclicrings may be unsubstituted, these compounds which have olefinicunsaturation, particularly multiple olefinic unsaturation, arepolymerizable and copolymerizable in known polymerization systems. Theyare particularly good crosslinking agents. These compounds are furtheruseful in the sense that they can be cleaved oxidatively, tocorresponding carboxylic acids, aldehydes and/or alcohols which haveknown utility in the plasticizer and detergent arts. The compounds whichdo not have olefinic unsaturation can also be oxidatively cleaved toproduce oxygenated, e.g., acid, alcohol or aldehyde, compounds havingknown utility.

4 Claims, No Drawings in turn is a continuation of Ser. No. 843,220 ofJuly 18, I

1969 now U.S. Pat. No. 3,586,727; 845,901 of July 29, 1969, now U.S.Pat. No. 3,629,347, and Ser. No. 845,904 of July 29,1969, now abandonedeach of which in turn is a continuation-in-part of Ser. No. 582,775 ofSept. 27, 1966, now abandoned.

the these parent applications, a process has been described for thecatalytic dimerizat ion and trimerization, respectively, of l,3-diolefins, in which catalysts are used which are produced by mixingcarbonylfree compounds of nickel with organometallic compounds such asmetal alkyls, metal aryls, or Grignard compounds, or with metal hydridesor with metal hydride complex compounds and electron donors. Theelectron donors used are Lewis bases such as cyclic ethers, tertiaryamines, especially cyclic tertiary amines, alkyl or aryl phosphines,especially triphenylphosphine, or alkyl or aryl phosphites or compoundswith a carbon-to-carbon multiple bond. Similar processes are claimed inGerman Auslegeschrift No. 1,126,864 of Badische Anilinund Sodafabrik,wherein the catalysts are made by the reduction of transitional metalcompounds by means of metals (Al, Mg), and German Auslegeschrift No.1,144,268, wherein certain nickel-(O) compounds are used as catalysts.Furthermore, it is known that butadiene can be transformed with the aidof catalysts, such as (R P) Ni(CO) into mixtures of cyclooctadiene-(1,5)and 4-vinylcyclohexene by the methods described in German Pat. No.881,511 and U.S. Pat. No. 2,686,209.

According to Austrian Pat. No. 232,495, the catalytic co-oligomerizationof butadiene and ethylene, for example, results in the formation ofcyclodecadiene- (l,5) compounds. According to all the processesdescribed in the above-cited patents, substituted 1,3- diolefms can beused instead of butadiene-(1,3).

This invention is for the production of large mono, bi or tricyclicalicyclic rings of the formula:

A B wherein:

0 is a member selected from the group consisting of cyclooctadiene-(1,5), cyclododecatriene-( 1,5 ,9), cyclodecadiene and cylodecatriene;

A is a member selected from the group consisting of methyl, ehtyl,vinyl, phenyl, buten-l-yl, buten-2-yl, methoxy and carboalkoxy having upto carbon atoms and;

B is a member selected from the grouo consisting of hydrogen, methyl,ethyl, vinyl and a carboalkoxy of up to 10 carbon atoms wherein:

A and B can be linked together by a bridge of the formula:

wherein:

When A is methyl and 0 is a cyclooctadiene, said methyl is attached to asaturated carbon atom in said cyclooctadiene ring and provide furtherthat where B is methyl, or a carboalkoxy group, A is methyl.

The products of this invention are made by the cyclooligomerization ofat least two different conjugated dienes. There may also be presentduring the cyclooligomerization one or more other olefinicallyunsaturated monomers which cyclocooligomerize along with the conjugateddienes. Large, multicyclic rings are produced in this latter fashion.

The cyclo-cooligomerization of this invention can be performed with theaid of catalysts of zerovalent nickel such as those described in GermanAuslegeschrift No. 1,140,569 and in Austrian Pat. No. 232,495. Thesecatalysts are especially well suited to use in thecyclocooligomerization of this invention since with these catalystsisomerizations of the types which have been observed to a certain extentin the case, for example, of catalysts prepared by means of alkalimetals according to German Auslegeschrift No. 1,126,864 do not occur.

The carbonyl-free zerovalent nickel catalysts used in this inventionhave the additional advantage in the cyclo-co-oligomerization processthereof in that they are catalytically active at lower temperaturesthan, for example, the catalysts which are prepared according to GermanAuslegeschrift No. 1,144,268.

The complex compounds of zerovalent nickel described in GermanAuslegeschrift No. 1, 191,375 can also be used as catalysts. In al casesin which substituted conjugated diene starting materials are used, thesubstituents themselves can be hydrocarbons or functional groups (e.g.,alkoxy or carboxylic acid ester groups). They may also be hydrocarbonswhich contain such functional groups. The only functional groupsinvolved are those which do not enter into any reactions with thecatalysts, with the conjugated diene or other reactants or with theunsaturated multicyclic products under the cyclo-co-oligomerizationreaction conditions hereof.

The process according to the invention can be performed in the presenceof inert solvents, but only those solvents which attack neither thereactants nor the products, nor the catalysts, nor the organometalliccomponents, nor the metal hydrides which were used for the manufactureof the catalysts are suitable. Aliphatic or aromatic hydrocarbons, oraliphatic or cycloaliphatic ethers are used preferentially.

It is particularly advantageous, however, to use the starting conjugateddiolefms or the products that can be made according to the process ofthis invention as solvents in the manufacture of the catalyst, so that aminimum of foreign substances will have to be separated from thereaction product. The process of this invention can be performed atnormal pressure of at elevated pressure. The pressure range in that caseis determined by the desired direction of the reaction and by thetemperature that is needed in each case. The process can be performed attemperatures from l0 to 200C, but preferably at 20 to C.

Multicyclic, unsaturated, hydrocarbon alicyclic rings can be producedaccording to the process of this invention in high yields with referenceto the non-conjugated diene reactant. The compounds that can bemanufactured according to the invention are valuable starting productsfor further syntheses. They can themselves be It is surprising that thecyclocooligomerization profurther cyclo-co-oligomerized to highermolecular ceeds very smoothly with very high conversions of the weightcompounds which are resinous in nature and are acrylic ester to thedesired cyclic product with little or therefore suited to use as moldingmaterials. They can no attack on the carboalkoxy group and little or nobe hydrogenated to saturated compounds and as such 5 conversion to openchain compounds. [t is believed used as solvents. They can beoxidatively cleaved at that this direction of the reaction is due to theparticuone or more unsaturated site to form aldehydes, alcolar catalysting used- Th e catalysts r p Se hols or acids which are themselvesuseful in a manner known materials and are themselves e j t Of and forapplications known t be tt ib d to h other patents and patentapplications of one or both of functional groups. the inventors hereof.These catalysts are defined as Through the co-oligomerization of cyclicacetylenes non-carbonyl'comaining zerovalent Pickel complex with b t di4 5- l h l l i compounds. In particular, zerovalent nickel complexes(l,4,7) can be pr d d i i ld f more h 95 f of nickel with electrondonors such as phosphines, the reacted l lki phosphites, and multipleolefins are preferred. The

wherein: reaction of this invention is schematically illustrated R, R',R' and R are each hydrogen or a subs'tanb l tially inert substituentsuch as an alkyl group, e.g., a lower alkyl group of up to about 8carbon atoms, an aryl group, e.g., a mono or dicyclic phenyl orsubstituted phenyl moiety having up to about 16 carbon i atoms, analkoxy or aryloxy group or possibly one or 9 LnXore halo groups alone oron an alkyl, alkoxy or aryl- CH CH c o R y group. 4 in an entirelyanalogous manner, one or more olefini- 4 cally unsaturated rings (wherethe olefinic unsaturation --I- is not or the conjugated diene type)cyclo-co-oligomer- R ize with butadiene or a substituted butadiene toform 1 3 an unsaturated multicyclic product. In accord with the practiceof this invention the conjugated diene reactant or reactants arecyclo-co-oli- 2 Z gomerized with one or more cyclic non-benzenoid un- 2saturated compounds as olefins which are not conju- R R gated dienes oras acetylenes in a reactant mole ratio 1 R such that there is preferablyone mole of cyclic reactant 3 to two moles of conjugated reactant. Whilethese mole ratios are preferred, it will be clear to one skilled in thisart that rectant proportions as low as 10 mole percent R of one type ofreactant to 90 percent of the other type R of reactant are suited to usein this invention. Where more than one representative of either type ofreactant is used, the individual compounds may be present in where R isan alkyl group, straight or branched chain, mole ratios of about 1 10 to10: l with respect to each preferably having up to about 8 carbon atomsand other where these are two reactants of one group. wherein R R R andR are the same or different and Where these are more than two reactantsof a given may be hydrogen,alkyl, aryl,alkoxy, halo, haloalkyl, orgroup, each reactant should represent at least 10 mole the like Alkyl lkor h l lk groups i bl percent of its entire group. It is preferred thatone h up to about 8 carbon atoms i t i ht or conjugated diene react withone cyclic unsaturate in br nched chain configuration. Aryl or aryloxygroups R-O-C the above-recited mole ratio of about 2 1 P suitably haveone or two fused or unfused phenyl rings, lypreferably one, and may haveone or several alkyl and- Another aspect of this invention is thecyclo-co-oli- /or halo substituents on one or more of the rings.gomerization of at least one conjugated diene with an Substituted 10member rings can be produced by the alkyl acrylate to form a lO-memberedolefinically unprocess of the invention in high yields with reference tosaturated alicyclic ring compound with a carboethoxy the acrylatereactant. The compounds that can be manpendant group thereon. ufacturedaccording to the invention are valuable start- The following areillustrative of the conjugated dienes which are useful in thisinvention: butadiene, isoprene, piperylene, chloroprene, ethylbutadiene, ethyl sorbate, phenyl butadiene, etc. The following areillustrative of the acrylates which are useful: methyl acrylate, ethylacrylate, n-butyl acrylate, Z-ethyl hexyl-acrylate, acrylonitrile, etc.

The acrylate monomer and the conjugated diene monomer are suitablyadmixed in mole ratios of about 1 to 10 1, preferably about 1 2. Wheredifferent conjugated dienes and different acrylates are cooligomerized,each member of the group should constitute at least about of its group.lt'is preferred that where several members of each group are used eachbe employed in substantially equal proportions.

Substituted l2-member rings are .obtained, for example, by thesimultaneous reaction of butadiene and isoprene in the presence ofcarbonyl-freecatalysts of zero valent nickel.l-Methyl-cyclododecatriene-( 1,5,9) is formed to a major extent, alongwith a little dimethylcyclododecatriene-( l ,S,9), and somecyclododecatriene( 1,5 ,9).

if butadiene is introduced into a solution of a catalyst nickel-(O)tri-(O-phenylphenyl)-phosphite l l in isoprene; a substituted ringcompound [l-methylcyclooctadiene-( l ,5)] forms in yields close to 90percent of the reacted isoprene.

According to the invention, many different subsitituted8, l0, andlZ-member rings can be produced by cyclocooligomerization, reactiondiagrams:

according to the following R R R R =l-l or aryl, alkyl or alkoxyradicals; in all of the above formulae at least one R is not hydrogen.

R R1 R Ah R R R R R H or aryl, alkyl or alkoxy radicals; in all of theabove formulae at least 1 'R is not hydrogen.

According to the invention, another type of cyclocooligomerization of1,3-diolefins can be achieved, namely, the cyclocooligomerization ofl-disubstituted conjugated dienes with 2- or 2,3-disubstitutedconjugated dienes.

R R and R aryl or alkyl, or R and R H.

. Substituted 8, l0, and l2-member rings can be produced by the processof the invention in high yields with reference to the substitutedbutadiene-(1,3) reactant. The compounds that can be manufacturedaccording to the invention are valuable starting products for furthersynthesis. For example, l-substituted and 1,2-disubstitutedcyclooctadienes and cyclododecatrienes, as well as 4,5dimethyl-cyclodecatrienes- (1,4,7) can easily be partially hydrogenatedto form the corresponding l-disubstituted and 1,2-disubstitutedcyclomonoolefins, respectively.

In addition to the cyclocooligomerization of two different conjugateddienes, such as butadiene and isoprene, according to this invention,another aspect of this invention resides in the cyclocooligomerizationof two different conjugated dienes and an additional unsaturatedcopolymerizable monomer or monomers which additional monomer or monomersare acetylenically or olefinically unsaturated but are not themselvesconjugated dienes. Thus, according to this aspect of this invention, twoor more different conjugated dienes, preferably two, arecyclocooligomerized under the same reaction conditions and catalyst asset forth above, with a monoolefinic or acetylenic comonomer to form asubstituted alicyclic compound having at least 10 carbon atomsand atleast two locations of unsaturation in the ring, and at least onesubstituent pendent from the ring.

The additional (third) monomer may be one or more of the following typesof compounds: acetylene, substituted acetylene, e.g., butine-l ethylene,styrene, acrylonitrile, acrylic acid esters, and the like. Thecyclocooligomerization, in this aspect of this invention the portion ofthe additional monomer pendent from the unsaturation therein, will forman additional pendent substituent on the alicyclic product. Thus, ifbutadiene, isoprene and propylene, for example, were cyclocooligomerizedaccording to this invention, an alicyclic product having at least 10carbon atoms in the ring and at least two methyl groups pendent from thering would result. I

It is within the scope of this invention to utilize acyclic or cyclicunsaturated reactants of the monounsaturated or conjugated diene type.

The substituted 8-, 10-, and 12-membered alicyclic rings, whether or notunsaturated, can be used as solvents.

Further, these unsaturated ring compounds can be oxidatively cleaved toproduce long-chain acids, aldehydes and alcohols-which have knownutility in the plasticizer and detergent arts.

This invention will be illustrated by the following examples in whichparts and percentages are by weight unless expressly stated to thecontrary.

EXAMPLE 1 4.34 g= 17.05 mmoles of nickel acetyl acetonate and 9.19 g17.05 mmoles of tri-(o-phenylphenyl)- phosphite are reduced in 85 cc ofbenzene in which about 10 g of butadiene are dissolved, with 4,43 g 34.1mmoles of monoethoxydiethyl aluminum, at to 20C. In two hoursapproximately 250 g of butadiene per hour (total 680g) are introducedinto the catalyst solution at 60C over a period of about 2 hours and 40minutes, with the simultaneous drop-by-drop addition of about 60 g ofisoprene per hour (total 165 g)..The reaction is interrupted, anddistillation is performed directly from the reaction vessel at torr anda bath temperature of no more than 100C. 766 g of'product are obtained,having the following compositions:

15.5 g 2.0% '4-vinylcyclohexene 4.3 g 0.6% mono-substituted4-vinylcyclohexene 5.2 g 0.7% p-diprene 610.0 g 79.7%cyclooctadiene-(LS) 119.5 g 15.6% 1-methylcyclooctadiene-(1,5)

7.4 g 0.9% dimethylcyclooctadiene-(1,5)

1.1 g 0.1% cyclododecatriene-(1,5,9)

1.8 g 0.2% 1-methylcyc1ododecatriene-(1,5,9)

0.7 g 0.1% dimethylcyclododecatriene-(1,5,9)

0.4 g 0.1% trimethylcyclododecatriene-( 1,5,9) The yield of1-methylcyclooctadiene-(1,5) amounts to 82 percent of the theory withreference to reacted isoprene (approximately 50 percent transformation).

The l-methylcyclooctadiene-(1,5) (B.P-. 595C, n 1.49.10), which has notbeen described hitherto, was characterized by infrared, H nuclearmagnetic resonance [NMR] and mass spectrometry. At normal pressure andC, it can easily bepartially hydrogenated to l-methylcyclooctene usingRaneyv nickel as the catalyst, with the absorption of 1 mole of HOxidative cleavage produces 8-ketononane-aldehyde.

EXAMPLE 2.

The same catalyst was manufactured as described above, but in isopreneinstead of benzene. For aperiod of 28 hours, at a reaction temperaturethat is slowly increased from to 52C, approximately 20 g of butadieneper hour are introduced (total about 600 g butadiene). Afterdistillationas in Example 1, 686 g of a productis obtained having thefollowing compositioni '-l 1.2 g= 1.6% 4-vinylcyclohexene 8.2 g 1.2%mono-substituted 4-vi'nylcyclohexene 4.5 g 0.7% p-diprene 517.0 g'=75.3% cyclooctadiene-(1,5)

125.7 g 18.3% l-methylcyclooctadiene-(1,5) 1

EXAMPLE 3 Catalyst (twice the amount) and procedure as in Example 1.Instead of the phosphite, however, the corresponding amount (4.45 g) oftriphenylphosphine is used. At a temperature of C approximately 30 g ofbutadiene per hour (total 250 g) are introduced into the catalystsolution and at the same time 25 g of isoprene [per hour] is added indrop-in-drop fashion. After distillation as in Example 1, 362 g ofproduct are obtained having the following composition:

61.6 g 17.0% 4-vinylcyclohexene 19.5 g 5.4% mono-substituted4-vinylcyclohexene f15.9' g 4.5% p-diprene 124.8 g 34.6%.cyclooctadiene-( 1,5

74.0 g 20.5% 1-methylcyclooctadiene-(1,5)

17.5 g 4.8% dimethylcyclooctadiene-(1,5)

7.7 g 2.2% cyclododecatriene-(1,5.9)

15.4 g 4.2% 1-methylcyclododecatriene-(1,5,9)

6.2 g 1.7% dimethylcyclododecatriene-(1,5,9)

4.1 g 1.2% trimethylcyclododecatriene-(1,5,9)

6.9 g= 1.9% higher oligomers The yield of 1-methylcyclooctadiene-(1,5),with reference to the reacted isoprene (37 percent transformation)amounts to 40 percent of the theory.

EXAMPLE 4 The catalyst (1.5 times the amount as in Example 1) isprepared in approximately one liter of piperylene' (740 g). For 28hours, approximately 45 g of butadiene per hour (total. 1280 g) areintroduced into this solution at a temperature of initially 44C andafter six hours finally at 50C. After distillation as in Example 1,1,642 g of product is obtained having the following composition:

22.9 g 1.4% 4-vinylcyclohexene 5.1 g 0.3% mono-substituted4-vinylcyclohexene 3.8 g 0.2% disubstituted 4-vinylcyclohexene 970.0 g59.1% cyclooctadiene-(l,5)

592.0 g 36.9% 3-methylcyclooctadiene-( 1,5)

44.0 g 2.6% dimethylcyclooctadiene-( 1,5)

4.4 g 0.3% higher oligomers The yield of 3-methylcycl'ooctadiene-( 1,5),with reference to the reacted piperylene (51 percent transformation),amounts to 86.4 percent of the theory.

EXAMPLE 5 Catalyst and procedure as in Example 1. 52 g of2-phenyl-butadiene are placed in the reaction vessel and 50 g ofbutadiene per hour are introduced for 6 hours at C. After distillation,342.4 g of product are obtained having the following composition:

9.5 g 2.8% 4-vinylcyclohexene 280.3 g 81.9%

cyclooctadiene-( 1,5

7.2 g 2.1% mono-substituted 4-vinylcyclohexene 42.2 g 12.3%l-phenylcyclooctadiene-(1,5)

3.2 g 0.9% higher oligomers 9 The yield of 1-phenylcyclooctadiene-.(1,5), with-reference to the reacted Z-phenyI-butadiene (transformation64 percent), amounts to 81 percent of the theory. Thel-phenylcyclooctadiene-(1,5) (B.P. -155C; n 1,5764) can be hydrogenatedcatalytically in part to phenyl-cyclooctane (B.P. 149C; n 1.5319).

EXAMPLE 6 Catalyst and procedure as in Example 1.

60.1 g of l-methoxy-butadiene are heated to 60C together with thecatalyst solution and for 20 hours approximately 30 g of butadiene perhour (total 620 g) are introduced. 661 g of a product are obtainedhaving the following composition:

16.6 g 2.5% 4-vinylcyclohexene 571.0 g 86.3% cyclooctadiene-(l,5)

1.6 g 0.2% mono-substituted 4-vinylcyclohexene 68.6 g 10.4%3-methoxycyclooctadiene-( 1,5)

3.0 g 0.5% higher oligomers The yield of 3-methoxycyclooctadiene-(1,5),with reference to the reacted l-methoxy-butadiene (transformation 85percent), amounts to 94 percent of the theory. This3-methoxycyclooctadiene-(1,5) B.P. 86C, n 1.4887) can easily behydrogenated catalytically with the absorption of 2 moles of H to formthe likewise previously undescribed methylcyclooctyl ether (B.P. 75 to76C, n 1.4578). Both compounds were characterized by their infrared, HNMR and mass spectra.

EXAMPLE 7 Catalyst (1,5 times the amount) and procedure as in Example 1.The catalyst solution is mixed with 122 g of-methyl-heptatriene-(1,3,6). At 60C, approximately 10 g of butadiene perhour were introduced for 28 hours (total about 290 g). 353 g areobtainedof a product having the following composition:

6.0 g 1.7% 4-vinylcyclohexene 238.0 g 67.5% cyclooctadiene-( 1,5)

3.3 g 1.2% mono-substituted 4-vinylcyclohexene 105.2 g 29.8%3-(butene-(l)-yl-(3)-cyclooctadiene- I EXAMPLE 8 Catalyst and procedureas in Example 1.

77.2 g of 2,3-dimethyl-butadiene are heated to C together with thecatalyst. For 16 hours, approximately 30 grams oof butadiene per hour(total 460 g) is intro- 10 duced, and 494.5 g of product is obtainedhaving the following composition:

1 1.9 g 2.4% 4-vinylcyclohexene 425.0 g 85.9% cyclooctadiene-(l,5)

50.4 g: 10.2%, 1,2-dimethyl-cyclooctadiene-(1,5)

4.2 g 0.8% disubstituted 4-vinylcyclohexene 3.0 g =0.6% higher oligomersThe yield of 1,Z-dimethyl-cyclooctadiene-(1,5), with reference to thereacted 2,3-dimethyl-butadiene (45 percent transformation), amounts to93 percent of the theory.

The 1,2-dimethyl-cyclooctadiene-( 1,5) B.P. 78.5C, n 1.4941), which hasnot been described hitherto, can easily be hydrogenated, with Raneynickel as the catalyst, partially to 1,2-dimethyl-cyclooctene, fromwhich n-decadione-(2,9) (MP 63 to 64C) is obtained by oxidativedecomposition.

EXAMPLE 9 Catalyst and procedure as in'Example 1.

232 g of n-octatriene-( 1 ,3,6) are heated with the catalyst solution toC, with the introduction of butadiene. In 1.5 hours, approximately 400 gof butadiene are absorbed. 527 g of product are obtained having thefollowing compositioni 8.7 g 1.6% 4-vinylcyclohexene 326.9 g 62.1%cyclooctadiene-(1,5)

11.3 g 2.1% monosubstituted 4-vinylcyclohexene 178.8 g 33.9%3-(butene-[2]-yl-[1])-cyclooctadiene-( 1,5)

-. 1.5 g 0.3% higher oligomers .The yield of 3-substitutedcyclooctadiene-( 1,5 with reference to the reacted n-octatriene-( 1,3,6)(transformation 55 percent), amounts to 93 percent of the theory.

Catalytic hydrogenation produces n-butyl-cyclooctane (B.P. 107C, 111.4609) with the absorption of 3 moles of H The hydrocarbon wasunequivocally characterized by its infrared and mass spectra.

EXAMPLE 10 The same catalyst as in Example 1 is reduced in a mixture of340 g of piperylene and 432 g of isoprene with the addition of 17 g ofbutadiene, and the reaction mixture is heated for 96 hours in anautoclave at 55 to 57C. After distillation as in Example 1, 713 g ofproduct are obtained having the following composition:

50.7 g 7.3% 5 unknown substance 14.4 g 2.1% 3-methylcyclooctadiene-(1,5)

15,0 g 2.2% p-diprene 24.4 g 3.5% 1-methylcyclooctadiene-(1,5)

22.5 g 3.2% 6 unknown substance 70.2 g 10.1%dimethylcyclooctadiene-(1,5) (from piperylene) 1,4- and 2,4-dimethylcyclooctadicue-(1,5)

86.3 g 12.5% cyclic and open-chain trimers 3.5 g 0.5% higher oligomers.

EXAMPLE 1 l 4.34 g 17.05 mmoles of nickel acetyl acetonate are reducedin 380 g of piperylene with 4.43 g 34.1 mmoles of ethoxy aluminumdiethyl. The catalyst solution is aspirated into an autoclave, and then50 g of butadiene and 50 atmospheres of ethylene are forced in. Everytwo days another 50 g of butadiene are forced in. The reaction mixtureis allowed to stand for 16 days at 12 to C. The excess ethylene andbutadiene is blown off and then hydrogen is immediately forced in underpressure. After no more l-l absorption is to be observed even at 60C and100 atmospheres hydrogen pressure, the autoclave is cooled and theexcess gas is blown off, and the entire reaction product is distilled.449 g of product are obtained, which, according to analysis by gaschromatography, has the following composition:

6.3 g 1.4% ethylcyclohexene 5.4 g 1.2% cyclooctane 24.3 g 5.4% n-decane263.0 g 58.5% cyclodecane 99.3 g 22.1% methylcyclodecane 1.8 g 0.4%dimethylcyclodecane 21.6 g 4.8% cyclododecane 16.6 g 3.7% higheroligomers The yield of methylcyclodecane (B.P., 92C) with reference toreacted piperylene (16 percent) amounts to about 75 percent.

EXAMPLE 12 23.4 g 9.4% n-decane 8.0 g 3.2% iso-undecane (methyldecane)2.0 g 0.8% dimethyl-n-decane 149.5 g 60.0% cyclodecane 39.7 g 15.9%methyl-cyclodecane 15.7 g 6.3% cyclododecane 2.0 g 0.8%methyl-cyclododecane 3.5 g 1.4% higher oligomers The yield ofmethyl-cyclododecane, with reference to the reacted isoprene (7percent), amounts to about 72 percent of the theory.

EXAMPLE 13 The catalyst is prepared as in Example 1 and mixed with 400 gof isoprene. 57 atmospheres of ethylene is forced onto the mixture in anautoclave, and then for hours about g of butadiene per hour areinjected. After cooling and blowing off to normal pressure, the reactionmixture is distilled as in Example 1. After hydrogenation under pressurewith Raney nickel catalyst, 682 g are obtained of a product having thefollowing composition:

10.2 g 1.5% ethylcyclohexane 8.2 g 1.2% n-decane 281.0 g 41.2%cyclooctane 68.2 g 10.0% methylcyclooctane 231.8 g 34.0% cyclodecane64.7 g 9.5% methylcyclodecane 8.2 g 1.2% higher oligomers The yield ofmethylcyclooctane and methylcyclodecane, with reference to the reactedisoprene (about 20 percent reacted), amounts to 91 percent of thetheory.

EXAMPLE 14 18 g= 65.5 mmoles of Ni(cyclooctadiene-[1,5]) are mixed in anautoclave with 1082 g of isoprene and 2000 g of butadiene and areallowed to stand for 2 months at 60C. After cooling, the catalyst in thereaction mixture is destroyed with 2N HCl with the admission of air.After distillation, 1383 g are obtained of a product of the followingcomposition:

5.5 g 0.4% two unknown hydrocarbons 47.6 g 3.3% 4-viny1cyclohexene 77.6g 5.6% p-diprene 35.8 g 2.6% cyclooctadiene-(1,5) 2.5 g 0.2% unknownhydrocarbons 27.7 g 2.0% dipentene 558.9 g 40.4% trans, trans,trans-cyclododecatriene-( 1,5,9)

21.6 g 1.6% trans, trans, cis-cyclododecatriene- 21.8 g 1.6% trans, cis,cis-cyclododecatriene- 224.7 g= 16.2% l-methyl-cyclododecatriene-(1,5,9)

80.4 g 5.8% l-methyl-cyclododecatriene-(1,5,9) II 17.2 g 1.2%dimethyl-cyclododecatriene-(1,5,9) l

7.3 g 0.5% dimethyl-cyclododecatriene-(1,5,9) 11 181.2 g 13.1% higheroligomers A portion of this product is hydrogenated, and by means ofpreparative gas chromatography methylcyclododecane is isolated (H020:1.4718). The hitherto undescribed 1-methylcyclododecatriene-(1,5,9) lboils at 14.5 torr at 118C. (n 1.5048). Thel-methylcyclododecatriene-(1,5,9) 11 was characterized only byhydrogenation to methylcyclododecane.

The yield of l-methyl-cyclododecatriene-(1,5,9), with reference toreacted isoprene (27 percent reaction), amounts to 40 percent of thetheory.

EXAMPLE 15 Catalyst and quantities of isoprene and butadiene as inExample 11.

The reaction mixture, however, is pumped through a reactor at 1 10C witha time of stay of about 60 minutes, the reactor consisting of a coppercapillary with a capacity of two liters which is lying in a heating bathand at the extremity of which there is installed a relief valve adjusted20-50 atmospheres. Total time 2.5 hours. The composition of the productsis similar to Example 14, but g of product is formed per hour per gramof nickel in the catalyst.

The yield of 1-methyl-cyclododecatriene-(1,5,9) amounts to 47 percent ofthe reacted isoprene (35 percent reacted).

Catalyst and procedure as in Example 14, but 1.08 kg of piperylene isused instead of isoprene. The reaction product obtained is agitated inair until it is virtually colorless. The nickel hydroxide thatprecipitates is separated by centrifu'gation and then distilled. 1514 gare obtained of a product having the following composition: v

1 19.2 g 7.9% 4-vinylcyclohexene 5.4 g 0.4% two unknown hydrocarbons I26.6 g 5.7% cyclooctadiene-(1,5)

1.7 g 0.1% 3-methyl-cyclooctadiene-(1,5)

73.7 g.= 4.8% five unknown hydrocarbons 1057.3 g 69.8% cyclododecatriene130.0 g 8.6% 3-methy1-cyclododecatriene-(1,5,9)

40.0 g 2.6% higher oligomers The yield of3-methyl-cyclododecatriene-(1,5,9), with reference to reacted piperylene(29 .percentreacted) amounts to 53 percent of the theory.

In the distillation, a 3-methyl-cyclododecatriene- (1,5,9) is obtained(B.F.' 105C, n 1.4968, 92 percent pure) which still has atcc-cyclododecatriene- (1,5,9)-content of 8 percent. Catalytichydrogenation yields methyl-cyclododecane in addition to cyclododecane.5 i

EXAMPLE 17 Catalyst as in Example lgAfter the addition of 100 g ofZOethylbutadiene, the mixture is heated to 60C and for 2 hoursapproximately 250 g of butadiene are introduced per hour. Afterdistillation as in Example 1 the following is obtained:

8.8 g 4-vinylcyclohexene 439.0 g cyclooctadiene-(l,5)

3.9 g ethyl-substituted 4-vinylcyclohexne 106.1 gl-ethyl-cyclooctadiene-(1,5)

3.6 g diethyl-cyclooctadiene-(11,5)

0.6 g cyclododecatriene-( 1,5,9)

2.3 g higher hydrocarbons 564.9 g product The yield of1-ethyl-cyclooctadiene-(1,5), with reference to reactedethylbutadiene(approximately 70 percent reacted), amounts to 95 percent of the theory.1

l-ethyl-cyclooctadiene-( 1,5 which has not been described hitherto,(8.11 76C, n 1,4900), was characterized by infrared, H NMR and massspectroscopy.

- EXAMPLE l8 Catalyst as in Example 1. but half the amount. At 80C,butadiene is introduced into the catalyst solution and simultaneously 55g of so rbic acid ethyl ester is added drop by drop over a period of 2hours. As the drop-by-drop addition is made, the' catalyst turns deepred and the butadiene absorptionv becomes slower. In hours approximately320 g of butadiene are reacted. After the usual distillation, thefollowing is obtained:

7.5 g 2.2% 4-vinylcyclohexene, 293.0 g 85.9% cyclooctadiene-(1,5)

3.9 g 1.1% six-ring codimers of butadiene and sorbic acid ethyl ester32.2 g 9.4% (8-methyl-cyclooctadienyl(3)-carboxylic acid ethyl ester l]4.7 g 1.4% higher olefins The yield of [1] amounts to 85 percent of thereacted sorbic acid ethyl ester (amount reacted 50 percent).

14 The 8-methyl-cyclooctadien( 1,5 )yl-( 3 )-carboxylic acid ethyl ester(B.P. 133C, n 1.484), which has not been described previously, wascharacterized by infrared, H NMR and mass spectra.

EXAMPLE 19 The catalyst was prepared by reducing 4.34 g 17.05 mmoles ofnickel acetyl acetonate and 9.19 g 17,05 mmoles of tri-(o-phenylphenyl)-phosphite in cc of benzene, in which about 10 g of butadiene aredissolved, with 4.43 g 34.1 mmoles of monoethoxydiethyl aluminum at 0 to20C.

This catalyst solution was heated together with 1 14 g of cyclododecineto 40C, and then for 20 hours, about 30 g of butadiene per hour were fedin. Thereafter, all volatile components of the reaction mixture weredistilled out at 10' torr and up to 40C. The distillation residue, whichcontained the catalyst in addition to the higher-boiling hydrocarbonproduct, was dissolved in 300 ml of pentane. The catalyst was destroyedby treatment with 2 N HCland excess air. The product of catalystdestruction, tri-(o-phenyl-phenyl) phosphite, is substantially insolublein pentane and was removed from the pentane solution by suctionfiltration. The resultant solution was cooled and concentrated to yield:

11.6 g 1.6% 4-vinylcyclohexene 569.4 g 78.8% cyclooctadiene-(1,5)

9.9g 1.4%unknown C to C range compounds 122.1 g 17.0%bi-cyclo-(10,8,0)-eicosatriene(cis,

cis, trans- A 3,7)

9.0 g 1.2% higher oligomers The yield of the novel bicycloeicosatriene,referred to the reacted cyclododecine (68% reacted), was 94% oftheoretical. I

The bicycloeicosatriene was characterized by infrared, Ram'an, arid byllnuclear magnetic resonance spectra and by chemical reactions. Partialhydrogenation over platinum in glacial acetic acid at atmosphericpressure yielded bicyclo-(10,8,0)-eicosadiene-(cis, cis, A",3) having amelting point of 775 to 80C. The' partial hydrogenated product was 98.6pure according to gas chromatography. Hydrogenation of the diene productover Raney nickel at 80C under hydrogen pressure yieldedbicyclo-(l0,8,0)-eicosene-(cis-A") having a melting point of 635 to 64C.The melting point of the bicycloeicosatriene was 89 to 94C, dependingupon the rapidity of heating, because of the rearrangement thereof to acis-divinylcyclohexene system. This rearrangement is observed in thecase of all cyclodeca-(1,5 )-dienes and cyclodeca-(1,4,7) trienes. Athigher temperatures the rearrangement is to 3,4-divinyl-bicyclo-(10,4,0)-hexadecene-(cis-A" which is partiallyhydrogenated to 3,4-diethyl-bicyclo-( l0,4,0)- hexadec'ene-(cis-A whichhas a boiling point of 135 to 139C at 10 torr anda refractioni'ndex u of1.5045. 1

EXAMPLE 20..

Approximately200 g of butadiene are introduced per hour into thecatalyst solution prepared according to Example 1, at 80 to C for aperiod of 3 hours. 'At' the same time, approximately 70 g ofbicyclo-(2,2,1)- heptene-(2) are added drop by drop. After vacuumdistillation according to Example 1, 636 g of product are obtained,having the following composition:

13.9 g 2.2% 4-vinylcyclohexene 448.0 g 70.4% cyclooctadiene-( 1 ,5)

0.6 g 0.1% cyclododecatriene-( 1,5,9)

6.6 g 1.2% two unknown hydrocarbons 119.8 g 26.1% tricyclo-(l0,2,l,0pentadecadiene-(cis, trans-4,8) f

This tricyclopentadecadiene partially isomerizes at high temperature toform cis-4,5-divinyl-tricyclo- (6,2,l,0 )-undecane (B.P. 147C, n1.5120). Hydrogenation with the absorption of 2 moles ofhydrogenproduces the corresponding cis-diethyl compound (B.P. 153C, n1,4934). Up'on catalytic hydrogenation over platinum in glacial aceticacid, the tricyclopentadecadiene (M.P.: 19.5 to 20C) yieldstricyclo-(10,2,1,0 ')-pentadecane (B.P. 167C, n :1.5ll0). f

All of the hitherto undescribedcompounds were characterized by theirinfrared and H NMR spectra.

The yield of tricyclo-pentadecadiene, with reference to reactedbicyclo-(2,2,1)-heptane-(2) (39v percent reaction), was 95 percent ofthe theory.

EXAMP E 21 e The catalyst was prepared as in Example 1. 36 g:= 191 mm ofcyclotetradecadiine( 1,8) were added to the catalyst solution andapproximately 50 g of butadiene per hour were introduced at 40C overabout hours; All of the volatiles (benzene, 4-vinylcyclohexene,cyclooctadiene-(l,5) were removed by vacuum distillation at 0.1 torr and20C. Approximately 500 rr il of benzene were added to the distillationresidue. The tricyclo(20,9,0"'0 )-triacontahexaene- (A"3,7,A' ,l 8,22)(1) that was formed is practically insoluble in benzene and thereforecan be removed by filtration. The catalyst was destroyed by shaking thebenzene solution with 2N aqueous l-lCl solution and with excess air.After drying with calcined N a SO;,, the benzene was distilled off atreduced pressure. The residue was taken up in a little pentane,whereupon thetri-(o-phenylphenyl)-phosphate, being insoluble, isleftbehind. After the pentane -is removed by distillation,bicyclo-.(12,8,0)-eicosatriene(A",3,7') ine-(16) (I1) and unreactedcyclotetradecadiine are separated byfractional crystallization from anether alcohol mixture. The following product distribution'was obtained:

35.5 g 2.7% 4-vinylcyclohexene 1218.0 g 94.2% cyclooctadiene-( 1 ,5)

10.0 g 0.8% higher oligomers and residue I 2 Substances (l) and ,(II)were formed ina yield of 9.3 percent with,reference to thecyclotetradecadiine that reacted (conversion 45 percent). 5

Substance l) has a melting point of l60-164C, and Substance (ll has amelting point-of 98-101C.Substances (l) and (II) have been characterizedby H NMR and infrared spectra. The partial hydrogenation of Substance(1) yields Tricyclo-(20,8,0,0 )-triacontadiene-(A"', A and the partialhydrogenation of Substance i.io

(11) yields" bicyclo-(l2,8,0)'docosene- EXAMPLE 22 The catalyst wasprepared by reducing 4.34 g 17.05 mmoles of nickel acetyl acetonate and9.19 g 17.05 mmoles of .tri-(o-phenylphenyl)-phosphite in cc of benzene,in which about 10 g of; butadiene are dissolved, with 4.43 g 34.1 mmolesof monoethoxy diethyl aluminum at 0 to 20C. After the addition of 34 gof acrylic acid ethyl ester, approximately 25 g of butadiene wereintroduced at 60C for 20 hours. After the customary distillation, thefollowing is obtained after hydrogenation:

6.3 g 2.1% ethylcyclohexene 233.8'g 79.0% cyclooctane 17.8 g 6.0%cyclodecanecarboxylic acid ethyl ester 2.7 g 0.9% undecanic acid ethylester 35.3 g 11.9% residue. t

EXAMPLE 23 A.solution of 4.46 g 17.05 mm of Ni(cyclooctadiene-(1,5)) and9.18 g 1705 mm of tri-(o-phenylphevnyl)-,phosphite in benzene containingbutadiene is used as .the catalyst. For 10 hours, at 80C, approximatelyg of butadiene are added per hour, and at the same time, a total ofabout 50 g of acrylic acid ethyl ester are added drop by drop, After thecustomary distillation and hydrogenation, the following is obtained:

16.1 g 1.9% ethylcyclohexane 740.0 g 86.6% cyclooctane 77.1 g i 9.0%cyclodecanecarboxylic acid ester 4.1 g= 0.5%(cis-3,4-diethyl-cyclohexenyl)-carboxylic acidethyl ester 9.3 g 1.1%u'ndecanic acid ethyl ester 8.2 g 1.0% residue and higher 'oligomers Weclaim:

1. A large bicyclic ring compound of the formula wherein 0 iscyclodecatriene-1,4,7 wherein A and B together form a group at the 1,2position of the cyclodecatrinene.

3. A large tricyclic ring compound of the formula wherein 0 1scyclodecatriene 1,4,7 wherein A and B together form a group at the 1,2position of the cyclodecatriene.

4. A large ring compound of the formula A-O-B wherein 0 iscyclodecatriene 1,4,7 wherein A is 4-ethyl.

UNITED STATES PATENT AND TRADEMARK OFFICE CETIFICATE OF CORRECTIONPATENT NO. 3 ,929,922 DATED December 30, 1975 VENTOR(S) I Gunther WilkeIt is certified that error appears in the ab0veidentified patent andthat said LettersPatent are hereby corrected as shown below:

Colo l line 53 "grouo should be group".

Col, 2 line 34 "a1" should be "all".

Col, 4, line 58 After "alkoxy" insert aryloxy Col. 5, line 6 "perfum"should be "perfume".

Col, 9, line 68 "00f" should be "of".

C01.: 15 line 32 "(2o,9,0 0 should be "(20,s,0 0

Signed and Scaled this Tenth Day of August 1976 [SEAL] Arrest:

RUTH C. MASON Arresting Officer

1. A LARGE BICYCLIC RING COMPOUND OF THE FORMULA
 2. A large bicyclicring compound of the formula A- theta -B wherein theta iscyclodecatriene-1,4,7 wherein A and B together form a
 3. A largetricyclic ring compound of the formula A- theta -B wherein theta iscyclodecatriene 1,4,7 wherein A and B together form a
 4. A large ringcompound of the formula A- theta -B wherein theta is cyclodecatriene1,4,7 wherein A is 4-ethyl.